Topology‐Oriented Crystalline Architectures of Metal Oxides for Advanced Electrocatalytic Water Splitting

ABSTRACT

Electrocatalytic water splitting remains a cornerstone strategy for sustainable hydrogen production; however, its overall efficiency is restricted by the sluggish oxygen evolution reaction. Metal oxides have emerged as highly promising catalysts owing to their adaptable electronic structures, high chemical stability, and abundant redox‐active sites. The crystal topology and phase symmetry fundamentally determine how these oxides conduct charge, expose active facets, and accommodate reaction intermediates. However, previous studies have mainly focused on individual phases or isolated materials, lacking a broader understanding of how topology‐governed coordination geometries and interfacial attributes collectively regulate the catalytic landscape. This review provides a comparative structural perspective on six representative crystalline families: perovskite, spinel, pyrochlore, tungsten bronze, fluorite, and garnet. These architectures offer distinct frameworks for tuning orbital overlap, controlling lattice distortion, and facilitating dynamic redox transitions, all of which influence catalytic reactivity. Additionally, structure‐derived descriptors, such as bond valence asymmetry, coordination‐induced orbital polarization, and symmetry‐governed charge redistribution, are discussed to clarify the effect of different crystalline matrices on the energetics and durability of electrocatalytic water splitting. This review aims to bridge crystallographic topology and electrocatalytic performance, offering design guidance for next‐generation oxide‐based catalysts suitable for industrial water splitting.